JPS61136513A - Production of epoxy resin having low temperature hydrolyzable chlorine content - Google Patents
Production of epoxy resin having low temperature hydrolyzable chlorine contentInfo
- Publication number
- JPS61136513A JPS61136513A JP60271695A JP27169585A JPS61136513A JP S61136513 A JPS61136513 A JP S61136513A JP 60271695 A JP60271695 A JP 60271695A JP 27169585 A JP27169585 A JP 27169585A JP S61136513 A JPS61136513 A JP S61136513A
- Authority
- JP
- Japan
- Prior art keywords
- hydrolyzable chlorine
- solvent
- epoxy resin
- chlorine content
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（発明の背景）
本発明は多価フェノールと多価アルコールのグリシジル
エーテルに関する。BACKGROUND OF THE INVENTION The present invention relates to glycidyl ethers of polyhydric phenols and polyhydric alcohols.
多価アルコールと多価フェノールのグリシジルエーテル
は一般にアルコール又はフェノールをエビクロロヒドリ
／と反応させてクロロヒドリ／エーテルを生成した後こ
れをデヒドロハロゲン化してグリシジルエーテルとして
製造される。Glycidyl ethers of polyhydric alcohols and polyhydric phenols are generally produced as glycidyl ethers by reacting alcohols or phenols with shrimp chlorohydrides to produce chlorohydrides/ethers, which are then dehydrohalogenated.
υ
クロロヒドリンエーテル基の不完全デヒドロノ・ロゲン
化は生成物中に塩素の残留となり、上記残留塩素は加水
分解性塩素又は活性塩素という。この残留加水分解性塩
素はたとい０・ｉｉｔ％又はそれ以下の少量でも硬化樹
脂の多くの用途における性質、特に電気的性質に有害と
なる。υ Incomplete dehydronorogenation of chlorohydrin ether groups results in residual chlorine in the product, and the residual chlorine is called hydrolyzable chlorine or active chlorine. This residual hydrolyzable chlorine, even in small amounts of 0.iit% or less, is detrimental to the properties of the cured resin in many applications, especially its electrical properties.
多価フェノールのグリシジルエーテルの製法は米国特許
第２．８０１．２２７号に記載されている。多価フェノ
ールを過剰のエピクロロヒドリンにとかしえ７を溶液を
約１００℃に加熱し苛性水浴液を加える。添加中エピク
ロロヒドリンと水が留出し留出物から水を分離しエピク
ロロヒドリンを反応機にもどす。反応終了時エビクロロ
ヒドリ／を蒸留除去し樹脂を炭化水素浴媒にとかし反応
で生成した塩を戸別する。欠いて溶媒を蒸留除去して少
なくも約０．２５％の加水分解性塩素含量をもつグリシ
ジルエーテルをえる。A method for preparing glycidyl ethers of polyhydric phenols is described in US Pat. No. 2,801,227. Dissolve the polyhydric phenol in excess epichlorohydrin, heat the solution to about 100°C, and add a caustic water bath. During the addition, epichlorohydrin and water are distilled out, the water is separated from the distillate, and the epichlorohydrin is returned to the reactor. At the end of the reaction, shrimp chlorohydrin/ is removed by distillation, the resin is dissolved in a hydrocarbon bath medium, and the salt produced by the reaction is sent to each house. The solvent is then distilled off to yield a glycidyl ether having a hydrolyzable chlorine content of at least about 0.25%.
米国特許第３．３０９．３８４号は米国特許第２，８０
１゜２２７号に記載と同じ多価フェノールのグリシジル
エーテル製造法を記載している。しかしデヒドロハロゲ
ン化反応とエピクロロヒドリン除去の後、樹脂状生成物
をメチルイソブチルケトンにとかし水を加えてとかし塩
を洗う。水と塩を分けた抜水酸化ナトＩＪウムを加えて
第２デヒドロハロゲン化反応をさせる。洗浄、中和、溶
媒除去後見られたグリシジルエーテルは０．１重量％以
下の加水分解性塩素含量をもつとわかったのである。U.S. Patent No. 3,309,384 is U.S. Patent No. 2,80
The same method for producing glycidyl ether of polyhydric phenol as described in No. 1゜227 is described. However, after the dehydrohalogenation reaction and epichlorohydrin removal, the resinous product is dissolved in methyl isobutyl ketone and water is added to wash the salt. A second dehydrohalogenation reaction is carried out by adding sodium hydroxide from which water and salt have been separated. The glycidyl ether found after washing, neutralization, and solvent removal was found to have a hydrolyzable chlorine content of less than 0.1% by weight.
米国特許第３．４１７．Ｏｓ ｏ号にエピクロロヒドリ
ンと多価フェノールの俗歌を炭化水素中に分散した苛性
微粒との反応による製法が記載されている。０．０７重
量％程の低加水分解性塩素含量をもつグリシジルエーテ
ルが生成される。U.S. Patent No. 3.417. No. 2007 describes a method for producing it by reacting epichlorohydrin with caustic fine particles dispersed in a hydrocarbon. Glycidyl ethers with hydrolyzable chlorine contents as low as 0.07% by weight are produced.
カナダ特許第５１３．３８８号は多価アルコールのグリ
シジルエーテルの製法を記載している。多価アルコール
のクロロヒドリンエーテルは３ふつ化はう素触媒を用い
て多価アルコールとエピクロロヒドリンの反応により製
造される。Canadian Patent No. 513.388 describes a process for making glycidyl ethers of polyhydric alcohols. Chlorohydrin ether of a polyhydric alcohol is produced by the reaction of a polyhydric alcohol and epichlorohydrin using a borohydride catalyst.
生成されたクロロヒドリンエーテルはアセトンにとかさ
れ苛性でデヒドロハロゲン化され見られるグリシジルエ
ーテルは０．５％以下の加水分解性塩素含量をもつ。The chlorohydrin ether produced is dissolved in acetone and dehydrohalogenated in a caustic solution, resulting in a glycidyl ether with a hydrolyzable chlorine content of less than 0.5%.
米国特許第４・４４７．５９８号は加水分解性塩素含有
グリシジルエーテルをトルエンとメチルエチルケトン溶
媒混合物中にとかした後苛性水溶液と反応させてグリシ
ジルエーテルの加水分解性塩素を３００ ｐｐｍ以下に
減少する方法を詳細記載している。U.S. Pat. No. 4,447,598 discloses a method for reducing the hydrolyzable chlorine content of glycidyl ether to 300 ppm or less by dissolving the hydrolyzable chlorine-containing glycidyl ether in a toluene and methyl ethyl ketone solvent mixture and then reacting it with a caustic aqueous solution. Details are listed.
特ＩＪ昭５８−２４５７８号はグリシジルエーテルをポ
リオキシアルキレングリコール又はクラウンエーテル溶
媒中アルカリ金属水酸化物で第２デヒドロハロゲン化し
て多価フェノールのグリシジルニーチルの加水分解性塩
素含量を０・ｌｉｔ：％以下に減少している。Special IJ No. 58-24578 discloses that the hydrolyzable chlorine content of glycidyl nityl, a polyhydric phenol, is reduced to 0.lit by converting glycidyl ether into secondary dehydrohalogenation with an alkali metal hydroxide in a polyoxyalkylene glycol or crown ether solvent: % or less.
英国特許出願２，１２０．６５９Ａ号は多価フェノール
を七ル過剰のエピクロロヒドリンと環状又＃ｉ線状エー
テル、例えばジオキサン又はジェトキシエタンにとかし
た後アルカリ金属水酸化物と反応させる多価フェノール
の低加水分解性塩素含有グリシジルエーテルの製法を記
載している。British Patent Application No. 2,120.659A discloses that polyhydric phenols are dissolved in an excess of epichlorohydrin in a cyclic or linear ether, such as dioxane or jetoxyethane, and then reacted with an alkali metal hydroxide. A method for producing a low hydrolyzable chlorine-containing glycidyl ether is described.
（発明の概要）
本発明はエポキシ樹脂の加水分解性塩素含量減少法に関
する。SUMMARY OF THE INVENTION The present invention relates to a method for reducing the hydrolyzable chlorine content of epoxy resins.
本発明の方法を行なうに全樹脂重量を基準として０．０
３重食％を超える加水分解性塩素含量をもつエポキシ樹
脂を溶ａｉｉ量を基準として樹脂約５０乃至約９５重食
％の量でイソプロパノール又は第２級ブタノール溶媒中
にとかす。0.0 based on total resin weight when carrying out the method of the present invention.
An epoxy resin having a hydrolyzable chlorine content greater than 3% is dissolved in an isopropanol or secondary butanol solvent in an amount of about 50 to about 95% resin based on the amount of dissolved aii.
この液に各加水分解性塩素含量当り約１・２乃至約３３
当量のアルカリ金属水酸化物水溶液を加える。エポキシ
樹脂の加水分解性塩素含量が望む程度に減少するまで反
応体を加熱するのである。This liquid contains about 1.2 to about 33% of each hydrolyzable chlorine content.
Add an equivalent amount of aqueous alkali metal hydroxide solution. The reactants are heated until the hydrolyzable chlorine content of the epoxy resin is reduced to the desired extent.
アルコール溶媒を蒸発させ酸を加え未反応アルカリ金属
水酸化物を中和し生成アルカリ金属塩を水洗して低加水
分解性塩素含有エポキシ樹脂生成物が回収される。The alcohol solvent is evaporated, acid is added to neutralize the unreacted alkali metal hydroxide, and the resulting alkali metal salt is washed with water to recover a low hydrolyzable chlorine-containing epoxy resin product.
加水分解性塩素デヒドロハロゲン化反応の溶媒としてイ
ソプロパノール又は第２級ブタノールを使えば加水分解
性塩素含量低くまたエポオキシド当量増加と粘度増加の
最も小さいエポキシ樹脂かえられる。If isopropanol or secondary butanol is used as the solvent for the hydrolytic chlorine dehydrohalogenation reaction, an epoxy resin with a low hydrolyzable chlorine content and minimal increase in epoxide equivalent and viscosity can be obtained.
（発明の説明）
本発明に便利なエポキシ樹脂は多価アルコールと多価フ
ェノールのグリシジルエーテルである。多価フェノール
のグリシジルエーテルは一般に反応触媒としてま友デヒ
ドロハロゲン化剤として苛性を用いて多価フェノールを
過剰のエピクロロヒドリン中で反応させて製造される。DESCRIPTION OF THE INVENTION Epoxy resins useful in the present invention are glycidyl ethers of polyhydric alcohols and polyhydric phenols. Glycidyl ethers of polyhydric phenols are generally produced by reacting polyhydric phenols in excess epichlorohydrin using caustic as a dehydrohalogenating agent as a reaction catalyst.
このグリシジルエーテルとこの反応は米国特許第２，８
０１，２２７号、第３．２６８．６１９号および第３．
３０９，３８４号に記載されており、これらの特許は参
考として本明細書に加えておく。This glycidyl ether and this reaction are described in U.S. Pat.
No. 01,227, No. 3.268.619 and No. 3.
No. 309,384, these patents are incorporated herein by reference.
多価アルコールのグリシジルエーテルは一般に触媒とし
てルイスの酸を用いて多価アルコールをその水酸基と当
量のエピクロロヒドリンと反応させて製造される。生成
されたグロロヒドリンエーテルを溶媒にとかし苛性てデ
ヒドロハロケン化スる。このグリシジルエーテルとこの
反応は米国特許第３，０３３，８０３号とカナダ特許第
５１３，３８８号に記載されて２つ、これらは本明細書
に参考として加えておく。Glycidyl ethers of polyhydric alcohols are generally prepared by reacting the polyhydric alcohol with its hydroxyl groups and an equivalent amount of epichlorohydrin using Lewis' acid as a catalyst. The produced chlorohydrin ether is dissolved in a solvent and dehydrohalokenized using caustic. This glycidyl ether and this reaction are described in US Pat. No. 3,033,803 and Canadian Patent No. 513,388, both of which are incorporated herein by reference.
本発明の方法に使用するに好ましいエポキシ樹脂はエボ
オキシド当量約１８０乃至約２２０をもつｐ、ｐ′−ジ
ヒドロキシジフェニルプロパン又はいわゆるビスフェノ
ールＡのグリシジルエーテルおよびエボオキシド当量約
３５０乃至約４５０をもつテトラブロモビスフェノール
Ａのグリシジルエーテルである。一般にエポキシ樹脂は
約０．０３乃至約０．７０重量％、好ましくは約１．０
７乃至約０．３０重重量の加水分解性塩素含量をもつ。Preferred epoxy resins for use in the process of the invention are p,p'-dihydroxydiphenylpropane or so-called glycidyl ether of bisphenol A having an eboxide equivalent weight of about 180 to about 220 and tetrabromobisphenol A having an eboxide equivalent weight of about 350 to about 450. glycidyl ether. Generally, the epoxy resin is about 0.03 to about 0.70% by weight, preferably about 1.0% by weight.
It has a hydrolyzable chlorine content of 7 to about 0.30 wt.
本発明に規定される加水分解性塩素含量は次の分析方法
によって決定される◎
各５０ｐのエポキシ樹脂２試料を５００ｍエルレンマイ
ヤーフラスコ２個に秤量する。各フラスコにトルエン３
〇−１をとり更に２個のフラスコは白試験用とする。樹
脂液ができたとき０．ＩＮアルコール性水酸化カリウム
（メチルアルコールＩＬに水酸化カリウム５．６１ｇを
とかす）を正確に５０−をとり各フラスコに加える。各
フラスコに空気コンデンサーをつけ４フラスコをホット
プレート上においてしづ力）に還流させる。還流１５分
後２ラスコをホットプレートからおろしコンデンサーを
つけたまま室已に冷しもコンデンサーをとりはずし各フ
ラスコにメチルエチルケトン１００ｄ％加える。各フラ
スコにフェノールフタレイン指示薬６滴を加えて０．Ｉ
Ｎ塩酸で内容物を滴定する。終点はビンタが無色になる
１滴をとる。加水分解性塩素ｌ量を計算する。The hydrolyzable chlorine content as defined in the present invention is determined by the following analytical method. Two samples of 50 p each of epoxy resin are weighed into two 500 m Erlenmeyer flasks. 3 toluene in each flask
Take 〇-1 and use two more flasks for the white test. 0 when the resin liquid is made. Accurately 50 g of IN alcoholic potassium hydroxide (5.61 g of potassium hydroxide dissolved in methyl alcohol IL) is added to each flask. Attach an air condenser to each flask and place the four flasks on a hot plate to reflux. After 15 minutes of reflux, remove the two flasks from the hot plate, cool to room temperature with the condenser still attached, remove the condenser, and add 100 d% of methyl ethyl ketone to each flask. Add 6 drops of phenolphthalein indicator to each flask. I
Titrate the contents with N-hydrochloric acid. At the end point, take one drop until the slap becomes colorless. Calculate the amount of hydrolyzable chlorine.
Ｂ：白試験滴定−
８：試料滴定−
Ｎ：塩酸浴液規定数
Ｗ：試料重量ダラム
本発明に使われる溶媒はイソプロパノールと第２級ブタ
ノールである。これらは各々単独で使用できるが、溶媒
中のエポキシ樹脂の沼解度改良のためアルコールと液体
芳香族炭化水素又はメチルイソブチルケトンとの混合物
ヲ使つとよい。溶媒混合物の約７５重量％までが芳香族
炭化水素又はケトンであってよい。溶媒混合物は約１５
乃至約３５重量％がアルコールで残りが芳香族炭化水素
又はケトンであることが好ましい。好ましい芳香族炭化
水素はベンゼン、トルエン′Ｓ？よびキシレンでろつ、
トルエンが最もよい。不 −発明の方法を行なうに全浴
奴重量を基準として約５０乃至約９５重量％、好ましく
は約７５乃至約８５重量％のエポキシ樹脂を溶媒にとか
す。B: White test titration - 8: Sample titration - N: Specified number of hydrochloric acid bath liquid W: Sample weight Durham The solvents used in the present invention are isopropanol and secondary butanol. Each of these can be used alone, but a mixture of alcohol and liquid aromatic hydrocarbon or methyl isobutyl ketone is preferably used to improve the solubility of the epoxy resin in the solvent. Up to about 75% by weight of the solvent mixture may be aromatic hydrocarbons or ketones. The solvent mixture is approximately 15
Preferably, from about 35% by weight is alcohol and the remainder aromatic hydrocarbon or ketone. Preferred aromatic hydrocarbons are benzene and toluene'S? and xylene,
Toluene is best. In carrying out the method of the invention, about 50 to about 95 weight percent, preferably about 75 to about 85 weight percent of epoxy resin, based on the total bath weight, is dissolved in a solvent.
本発明に使用するアルカリ金属水酸化物はアルカリ金楓
水酸化物約３０乃至約７０ｘｉｉｋ％、好ましくは約４
５乃至約５５重量％をもつ水溶液である。好ましいアル
カリ金属水酸化物は水酸化カリウムと水酸化ナトリウム
でおり、水酸化ナトリウムが最もよい。The alkali metal hydroxide used in the present invention is about 30 to about 70 xiik%, preferably about 4% alkali metal hydroxide.
5 to about 55% by weight. Preferred alkali metal hydroxides are potassium hydroxide and sodium hydroxide, with sodium hydroxide being the best.
本発明の方法を行なうに加水分解性塩素含有エポキシ樹
脂を溶媒にとかし友後アルカリ金属水酸化物水溶液を加
える。水酸化物は加水分解性塩素ｌ量当り約１．２乃至
約３３当量、好ましくは約１．２乃至約３．２５当量の
量で加える。昇温状態に加熱し加水分解性塩素が望む量
に減少するに十分を時間撹拌をつづける。一般に加熱は
約１３０乃至約２００下、好ましくは約１４０乃至約１
６０７の温度で行なう。時間は約３０分乃至約２時間で
よい。In carrying out the method of the present invention, a hydrolyzable chlorine-containing epoxy resin is dissolved in a solvent and then an aqueous alkali metal hydroxide solution is added. The hydroxide is added in an amount of about 1.2 to about 33 equivalents, preferably about 1.2 to about 3.25 equivalents per liter of hydrolyzable chlorine. Heat to elevated temperature and continue stirring for a sufficient time to reduce the hydrolyzable chlorine to the desired amount. Generally the heating is from about 130 to about 200, preferably from about 140 to about 1
607 temperature. The time may be about 30 minutes to about 2 hours.
反応完了の場合、即ち加水分解性塩素が望む点まで減少
した場合、この分野でよく知られた方法でエポキシ樹脂
を回収する。好ましい方法に２いて未反応アルカリ金属
水酸化物を稀砿酸水浴敷で中和し溶媒を蒸留除去する。When the reaction is complete, ie, the hydrolyzable chlorine has been reduced to the desired point, the epoxy resin is recovered by methods well known in the art. In a preferred method 2, the unreacted alkali metal hydroxide is neutralized with a dilute arsenic acid solution and the solvent is removed by distillation.
水を加えて塩を洗浄する。樹脂と水を加熱し撹拌し止め
て水層を分離しすてる。樹脂の塩がなくなるまで水処理
をつづける。Add water to wash the salt. Heat the resin and water, stop stirring, and separate the water layer. Continue water treatment until the resin salts are gone.
次の実施例は不発明を詳記している。特に断らない限り
部およびパーセントは重量基準である。The following examples detail the invention. Parts and percentages are by weight unless otherwise specified.
実施例り
適当する反応機にエボオキシド当量３７６．３００Ｔに
おける溶融粘度８０ ｃｐｓおよび加水分解性塩素含量
０．０７１％をもつテトラブロモビスフェノールＡのジ
グリシジルエ７−ルｌ ５００ Ｗ％イソプロパツール
５００部およヒドルエン５００部を加え九。溶液となつ
ｆＣ時５０％水酸化ナトリウム水溶ｆ３３部を加え次。Example 500 parts of diglycidyl alcohol 7-1 500 W% of tetrabromobisphenol A having a melt viscosity of 80 cps at an evoxide equivalent weight of 376.300 T and a hydrolyzable chlorine content of 0.071% and 500 parts of isopropanol are added to a suitable reactor. Add 500 parts of Hidruene and make 9. Next, add 33 parts of 50% sodium hydroxide aqueous solution to the solution.
加熱して１８０″Ｆ温度とし１時間保った後脱イオン水
１０００９を加えも加熱をつづけてトルエンとイソプロ
パノール溶媒を蒸留除去した。After heating to 180''F and holding for 1 hour, deionized water 10009 was added and heating continued to distill off the toluene and isopropanol solvents.
温度１８３下に遅し九とき撹拌をやめ２層に分かれさせ
池上の水層を出し更に１０００部の脱イオン水を加え池
温［１７８−１８１？で１５分撹拌して止め上の水層を
すてて９７０部の脱イオン水を加えた。加熱撹拌３０分
後止めて上の水層を捨て１０００部の脱イオン水を加え
も１７６−１９０７で３０分撹拌後止め上の水層をすて
ち水５０部中に０．ＩＮ塩ｔＲｇ、ｌ−３部のｇを加え
次いで１０００部の脱イオン水を加えｔム１８９−１９
０”Ｆで１５分間加熱撹拌後止めて中性ｐＨの上層をす
ても加熱し真空として水を除去し７０分後に温度３１０
？、真空４５ ｍａｙとなった。３１０？に３０分保っ
た抜水は完全に除去されもえられた生成物は０．００２
％の加水分所性塩素含量、４３５のエボオキシド当量お
よび１７０ ｃｐｓの３００？溶融粘度をもっていら
実施例１に使用したと同じエポキシ樹脂を用いて更に反
応を行なわせへ溶媒の量と盤並びに水酸化ナトリウム量
、反応温度と時間を変え友。実施例１と同じ方法で生成
物から塩と水酸化す） ＩＪウムを洗い回収し乾燥しも
反応の条件と結果を表に示している。表中”ｐｈデは樹
脂１ｏｏＶＬ童部当りの重量部を示す。When the temperature reaches 183 degrees, stop stirring and separate into two layers. Remove the water layer above the pond. Add 1000 parts of deionized water and add the pond temperature [178-181? After stirring for 15 minutes, the aqueous layer on top was discarded and 970 parts of deionized water was added. After heating and stirring for 30 minutes, stop the water layer, discard the upper water layer, add 1000 parts of deionized water, and stir for 30 minutes with 176-1907. Add IN salt tRg, l - 3 parts g then add 1000 parts deionized water tm 189-19
Heat at 0"F for 15 minutes, stir, then stop, heat the upper layer at neutral pH, apply vacuum to remove water, and after 70 minutes, temperature 310
? , the vacuum was 45 may. 310? The water was completely removed by keeping it for 30 minutes, and the product obtained was 0.002
% hydrophilic chlorine content, 435 eboxide equivalents and 170 cps. When the melt viscosity was determined, a further reaction was carried out using the same epoxy resin used in Example 1, changing the amount of solvent, amount of sodium hydroxide, reaction temperature and time. The reaction conditions and results are shown in Table 1. The salt and hydration of the product was carried out in the same manner as in Example 1.) IJium was washed, recovered and dried.The reaction conditions and results are shown in the table. In the table, "ph" indicates parts by weight per 10 VL part of resin.
実施例１２
適当する反応機にメチルイソブチルケト／中テトラブロ
モビスフェノールＡのジグリシジルエーテルの固体含量
７２．７％＃ｉ／［１３７６部を加えた。グリシジルエ
ーテルのエボオキシド当童は３６９であり加水分解性塩
素は０Ｄ２１％であった。浴液を１８０下に加熱しイソ
プロパノール８４部と５０％水酸化ナトリウム水溶液２
２部を加えた。Example 12 To a suitable reactor was added 1376 parts of the diglycidyl ether of methyl isobutyl keto/medium tetrabromobisphenol A with a solids content of 72.7% #i/[. The eboxide value of glycidyl ether was 369, and the hydrolyzable chlorine was 0D21%. Heat the bath solution to below 180℃ and add 84 parts of isopropanol and 2 parts of 50% sodium hydroxide aqueous solution.
Added 2 parts.
加熱撹拌１８０−１８２７で１時間２５分つづけ池水１
２２４部を加え丈に水９０部中硫酸１１゜１７部の溶敷
を加えた。１０分後更に水４４部に硫酸２．４３部の浴
液を加え友。添加５分後反応機内容物は中性ｐＨとなっ
旭反応機に真窒蒸留装置をつけた。＠度は３２５？とな
り４５部ｍＨｙ真空となつも２０分間真窒加熱後真窒を
止めトルエン２５０部を反応機に加えた。えた溶液をフ
ィルタープレスで濾過して塩を除去した。Pond water 1 for 1 hour and 25 minutes with heating stirring 180-1827
224 parts of the solution was added, and a solution of 11.17 parts of sulfuric acid in 90 parts of water was added. After 10 minutes, a bath solution of 2.43 parts of sulfuric acid was added to 44 parts of water. Five minutes after the addition, the contents of the reactor reached a neutral pH, and the Asahi reactor was equipped with a true nitrogen distillation device. @ Degree is 325? This resulted in a vacuum of 45 parts mHy and after heating with nitrogen for 20 minutes, the nitrogen supply was stopped and 250 parts of toluene was added to the reactor. The resulting solution was filtered using a filter press to remove salts.
反応生成物は３７６のエボオキシド当量と０．００９％
の加水分解性塩素含量をもっていｔム固体含量は８０％
であうｔム
上記明細畳に本発明の原理、好ましい実施態様および操
作方法を記述したのでおる。発表した特定形態は制限す
るよりは例証するためのものであるから、保護され窺い
と考える本発明は特定形態に限定されると解釈すべきで
はない。The reaction product has an eboxide equivalent of 376 and 0.009%
With a hydrolyzable chlorine content of 80% solids content
The principles, preferred embodiments, and method of operation of the present invention have been described in the above specification. The invention claimed to be protected should not be construed as limited to the specific forms presented, which are intended to be illustrative rather than limiting.
本発明の真意から逸脱しない限りこの技術分野の矧Ｒあ
る者によって種々の変更法も可能であろう。Various modifications may be made by those skilled in the art without departing from the spirit of the invention.
Claims (1)
価フェノールの誘導体であり少なくも約０．０７重量、
の加水分解性塩素含量をもつエポキシ樹脂をイソプロパ
ノール又は第２級ブタノールからなる溶媒中に樹脂と溶
媒の合計重量を基準として約５０乃至約９５重量、の量
で溶解し、（ｂ）これにアルカリ金属水酸化物水溶液を
エポキシ樹脂の加水分解性塩素当量当り水酸化物約１．
２乃至約３３当量の量で加え、かつ （ｃ）該反応体混合物を加水分解性塩素含量を減少する
に十分の時間加熱する 工程より成ることを特徴とする低加水分解性塩素含量を
もつエポキシ樹脂の製法。 ２、エポキシ樹脂がビスフェノールＡのジグリシジルエ
ーテルである特許請求の範囲第１項に記載の方法。 ３、エポキシ樹脂がテトラブロモビスフェノールＡのジ
グリシジルエーテルである特許請求の範囲第１項に記載
の方法。 ４、アルカリ金属水酸化物が水酸化ナトリウムである特
許請求の範囲第１項に記載の方法。 ５、溶媒が液体芳香族炭化水素とイソプロパノールの混
合物である特許請求の範囲第１項に記載の方法。 ６、芳香族炭化水素がトルエンである特許請求の範囲第
５項に記載の方法。 ７、溶媒が液体芳香族炭化水素と第２級ブタノールの混
合物である特許請求の範囲第１項に記載の方法。 ８、芳香族炭化水素がトルエンである特許請求の範囲第
７項に記載の方法。 ９、溶媒がメチルイソブチルケトンとイソプロパノール
の混合物である特許請求の範囲第１項に記載の方法。 １０、溶媒がメチルイソブチルケトンと第２級ブタノー
ルの混合物である特許請求の範囲第１項に記載の方法。[Scope of Claims] 1. (a) a derivative of epichlorohydrin and a polyhydric alcohol or a polyhydric phenol, at least about 0.07% by weight;
(b) an epoxy resin having a hydrolyzable chlorine content of about 50 to about 95 by weight, based on the combined weight of resin and solvent, is dissolved in a solvent consisting of isopropanol or secondary butanol; The metal hydroxide aqueous solution is mixed with about 1.0 hydroxide per equivalent of hydrolyzable chlorine of the epoxy resin.
2 to about 33 equivalents; and (c) heating the reactant mixture for a time sufficient to reduce the hydrolyzable chlorine content. Resin manufacturing method. 2. The method according to claim 1, wherein the epoxy resin is diglycidyl ether of bisphenol A. 3. The method according to claim 1, wherein the epoxy resin is diglycidyl ether of tetrabromobisphenol A. 4. The method according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide. 5. The method according to claim 1, wherein the solvent is a mixture of a liquid aromatic hydrocarbon and isopropanol. 6. The method according to claim 5, wherein the aromatic hydrocarbon is toluene. 7. The method according to claim 1, wherein the solvent is a mixture of liquid aromatic hydrocarbon and secondary butanol. 8. The method according to claim 7, wherein the aromatic hydrocarbon is toluene. 9. The method according to claim 1, wherein the solvent is a mixture of methyl isobutyl ketone and isopropanol. 10. The method according to claim 1, wherein the solvent is a mixture of methyl isobutyl ketone and secondary butanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/677,711 US4535150A (en) | 1984-12-04 | 1984-12-04 | Process for preparing epoxy resins having low hydrolyzable chlorine contents |
| US677711 | 1996-07-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61136513A true JPS61136513A (en) | 1986-06-24 |
| JPH0633330B2 JPH0633330B2 (en) | 1994-05-02 |
Family
ID=24719825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60271695A Expired - Lifetime JPH0633330B2 (en) | 1984-12-04 | 1985-12-04 | Process for making epoxy resins with low hydrolyzable chlorine content. |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4535150A (en) |
| EP (1) | EP0184431A1 (en) |
| JP (1) | JPH0633330B2 (en) |
| CA (1) | CA1252248A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01263111A (en) * | 1988-04-14 | 1989-10-19 | Mitsui Petrochem Ind Ltd | Production of polyhydric phenol epoxy resin |
| US7268192B2 (en) | 2003-02-17 | 2007-09-11 | Tohto Kasei Co., Ltd | Process for producing high-purity epoxy resin and epoxy resin composition |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617357A (en) * | 1984-09-24 | 1986-10-14 | Ciba-Geigy Corporation | Process for reducing the content of chlorine in glycidyl compounds |
| US4810776A (en) * | 1986-07-14 | 1989-03-07 | Ciba-Geigy Corporation | Process for producing epoxy resin having a low-EHC-content from chlorine-substituted crude epoxy resin of high EHC-content and apparatus for automatically controlling such process |
| CA1293837C (en) * | 1986-10-14 | 1991-12-31 | Ha Q. Pham | Preparation of epoxy resins |
| US5576362A (en) * | 1992-04-20 | 1996-11-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Insulating material and a circuit substrate in use thereof |
| US5969036A (en) * | 1997-06-20 | 1999-10-19 | The Dexter Corporation | Epoxy-containing die-attach compositions |
| WO2001042230A1 (en) | 1999-12-07 | 2001-06-14 | 3M Innovative Properties Company | Process for the elimination of materials containing hydrolyzable halides and other high molecular weight materials from epihalohydrin derived epoxy resins |
| US6211389B1 (en) | 2000-05-23 | 2001-04-03 | Dexter Corporation | Methods of reducing the chloride content of epoxy compounds |
| DE10208743A1 (en) * | 2002-02-28 | 2003-12-11 | Siemens Ag | Low corrosion epoxy resins and manufacturing processes |
| US20120190773A1 (en) * | 2007-11-09 | 2012-07-26 | Dalip Kumar Kohli | Composite surfacing film with ultraviolet light and abrasion resistance |
| CN114989394B (en) * | 2022-07-20 | 2023-09-19 | 智仑超纯环氧树脂(西安)有限公司 | Preparation method and application of low-chlorine epoxy resin |
| CN115073652B (en) * | 2022-07-20 | 2023-09-19 | 智仑超纯环氧树脂(西安)有限公司 | Polar adsorbent for removing chlorine from epoxy resin, preparation method thereof and method for preparing ultra-high purity epoxy resin by using polar adsorbent |
| CN114989396B (en) * | 2022-07-20 | 2023-09-19 | 智仑超纯环氧树脂(西安)有限公司 | Method for removing organochlorine impurities in epoxy resin through MOFs material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490400A (en) * | 1977-12-20 | 1979-07-18 | Shell Int Research | Preparation of polyglycidyl ethers |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA513388A (en) * | 1955-05-31 | J. O'boyle Charles | Polyether polyepoxides | |
| NL191641A (en) * | 1953-10-19 | |||
| US2943095A (en) * | 1955-06-28 | 1960-06-28 | Union Carbide Corp | Process for preparing glycidyl polyethers of polyhydric phenols |
| US3309384A (en) * | 1961-10-02 | 1967-03-14 | Celanese Coatings Co | Preparation of low viscosity epoxide resins |
| US3417050A (en) * | 1965-05-04 | 1968-12-17 | Celanese Coatings Co | Epoxide resin process |
| IT1012923B (en) * | 1974-05-30 | 1977-03-10 | Sir Soc Italiana Resine Spa | PROCEDURE FOR THE CONTINUOUS PREPARATION OF POLYGLYCLICIDYL ETHERS OF POLYOXYYL PHENOLS |
| CA1144933A (en) * | 1979-04-19 | 1983-04-19 | Johan Van Gogh | Process for the preparation of polyglycidyl ethers of polyhydric phenols |
| JPS5824578A (en) * | 1981-08-05 | 1983-02-14 | Mitsui Petrochem Ind Ltd | Preparation of glycidyl ether |
| GB2120659B (en) * | 1982-04-28 | 1985-12-04 | Sumitomo Chemical Co | Process for producing glycidyl ethers of monohydric polyhydric phenols |
| US4447598A (en) * | 1983-04-07 | 1984-05-08 | The Dow Chemical Company | Method of preparing epoxy resins having low hydrolyzable chloride contents |
-
1984
- 1984-12-04 US US06/677,711 patent/US4535150A/en not_active Expired - Lifetime
-
1985
- 1985-11-12 CA CA000495127A patent/CA1252248A/en not_active Expired
- 1985-12-03 EP EP85308803A patent/EP0184431A1/en not_active Withdrawn
- 1985-12-04 JP JP60271695A patent/JPH0633330B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490400A (en) * | 1977-12-20 | 1979-07-18 | Shell Int Research | Preparation of polyglycidyl ethers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01263111A (en) * | 1988-04-14 | 1989-10-19 | Mitsui Petrochem Ind Ltd | Production of polyhydric phenol epoxy resin |
| US7268192B2 (en) | 2003-02-17 | 2007-09-11 | Tohto Kasei Co., Ltd | Process for producing high-purity epoxy resin and epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0184431A1 (en) | 1986-06-11 |
| US4535150A (en) | 1985-08-13 |
| JPH0633330B2 (en) | 1994-05-02 |
| CA1252248A (en) | 1989-04-04 |
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